Herbicidal composition

ABSTRACT

A herbicidal composition comprises a bipyridylium salt and a thiocarbamate having the formula ##STR1## wherein R and R 1  each represent a lower alkyl group which in combination with each other can form a heterocyclic ring with the N atom; R 2  represents ##STR2## AND X represents a halogen atom or a lower alkyl group; and n represents 0, 1 or 2.

This application is a continuation of application Ser. No. 609,725, filed Sept. 2, 1975, now U.S. Pat. No. 4,028,091.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a new herbicidal composition which is effective for both foliage treatment and soil treatment in agricultural areas such as orchards, upland fields, paddy fields and the like, and also in non-agricultural areas.

2. Description of the Prior Art

In general, it takes relatively less time to cultivate an orchard as compared with the time required for cultivation in other agricultural areas. However, in many cases, the orchard is developed adjacent to a forest and/or a wasteland. In these situations, many weeds are extended from the forest and/or wasteland into the orchard. Accordingly, various weeds, such as annual weeds, e.g., Manna-grass, Barnyard grass, Smartweed, and the like; perennial weeds, e.g., Field horsetail, Culy dock, Cayratia Japonica, Bindweed, and the like, and coppice appear. Some of these weeds grow very high and/or in high multiplication. Some weeds appear in the areas immediately surrounding the trees. The following problems, associated with the yield of the fruit and the control and tending of the operation, are caused by the presence of these weeds:

(1) The control and tending operations are disturbed.

(2) The effects of the wind and sunlight are diminished.

(3) Disease and insect damage are caused and promoted.

(4) The nutritional value of fertilizer is lost.

(5) Water in the soil is used up, causing drought injury.

In the conventional methods of inhibition of the weeds, it has been known to apply foliage-treatment type herbicides such as 1,1'-dimethyl-4,4'-bypyridylium dichloride or a mixture of 3,4-dichloropropionanilide and α-naphthyl N-methylcarbamate in the growing period of the weeds, or to apply soil-treatment type herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea or 2,4-bis(iso-propylamino)-6-methylthio-1,3,5-triazine, and the like before the weed seedlings appear. When the soil-treatment type herbicides are applied, the active ingredient is translocated in the soil and is absorbed by the roots of the trees, causing phytotoxicity. Also, the herbicidal effect is disadvantageously varied by changing said conditions, such as the water content of the soil. On the other hand, when the foliage-treatment type herbicides are applied, the herbicidal effect is relatively stable and confirmation of its efficacy can easily be made. Retreatments can then be made accordingly. As a result, foliage-treatment type herbicides such as 1,1'-dimethyl-4,4'-bipyridylium dichloride and a mixture of 3,4-dichloropropionanilide and α-naphthyl N-methylcarbamate have been used primarily. However, when 1,1'-dimethyl-4,4'-bipyridylium dichloride is used, the herbicidal effect against grown weeds is inferior. It is considered that this defect is caused by small translocation of the active ingredient into the bodies of the plants. Only the cells of the weeds in the immediate vicinity of the point of contact of the active ingredient are damaged under conditions of intense irradiation. The translocation of the active ingredient in the weeds is quite slow, causing an inferior effect. The herbicidal effect is also disadvantageously decreased by rain-fall after the application. In such cases, the regrowth of the weeds is rapid, whereby the purpose of the application of the herbicide cannot be attained. Accordingly, sequential applications of the herbicides are necessitated. Consequently, a need continues to exist for an effective herbicide especially for use in an orchard against grown weeds.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a herbicidal composition which is effective for inhibiting the growth of weeds in the growth stage as well as weeds in other stages in both agricultural and non-agricultural areas, especially in orchards.

Briefly, this and other objects of this invention, as will hereinafter become clear from the ensuing discussion, have been attained by providing a herbicidal composition which comprises a bipyridylium salt of 1,1'-dimethyl-4,4'-bipyridylium or 1,1'-ethylene-2,2'-bipyridylium and a thiocarbamate having the formula ##STR3## wherein R and R₁ each represent a lower alkyl group having 1 - 7 carbon atoms which in combination with each other can form a heterocyclic ring with the N atom; R₂ represents ##STR4## wherein X represents a halogen atom such as F, Cl, Br or I, or a lower alkyl group, having 1 - 7 carbon atoms and n represents 0, 1 or 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The thiocarbamates used in this invention have a relatively low herbicidal effect in foliage treatment when used alone. Accordingly, heretofore, it has been considered nearly impossible to improve the herbicidal effect in foliage treatment by combination with other herbicides. The present invention has been attained by the discovery of a special synergistic effect resulting from the combination of the specific bypyridylium salts and the specific thiocarbamates mentioned above. The surprising synergistic effects imparted by the combination of these ingredients are as follows:

(1) The herbicidal drought effect of the specific bipyridylium salt when used alone is remarkably improved. Effective results can be attained by using an amount of the specific bipyridylium salt which is only 1/2 - 1/4 of the amount required when the salt is used alone.

(2) The herbicidal effect against weeds in the grown stage is remarkably improved. The weed-growth inhibiting period is prolonged by prevention of the regrowth of the weeds.

(3) The herbicidal effect is improved, even when it is applied under intense irradiation.

(4) The decrease in the herbicidal effect caused by rainfall after application is negligible.

It is considered that the above-mentioned effects are effected by promoting the absorption and translocation of the specific bipyridylium salt into the body of plants by synergistic action with the specific thiocarbamate, and also by promoting the herbicidal effect of the specific bipyridylium salt in the body of the plant. The specific thiocarbamate itself imparts a herbicidal effect in soil-treatment in addition to the above-mentioned synergistic effects to control the growth of weeds in the soil. Accordingly, the herbicidal composition of this invention is an ideal herbicidal composition for both foliage and soil-treatment. Among other things, the synergistic effects could not be expected because the specific thiocarbamate is a soil-treating agent and the herbicidal effect is produced by inhibition of protein production in plants.

In the herbicidal composition of this invention, the ratio of the bipyridylium salt to the thiocarbamate should be 1 : 1 ˜ 100, preferably 5 ˜ 30. In foliage treatment, the amount of the bipyridylium salt should be 5 - 500 g/10 ares, preferably 10 - 50 g/10 ares, and the amount of the thiocarbamate should be 20 - 500 g/10 ares, preferably 100-300 g/10 ares. In soil treatment, the amount of the pyridylium salt should be 5 - 500 g/10 ares, preferably 10 - 50 g/10 ares, and the amount of the thiocarbamate should be 50 -1000 g/10 ares, preferably 200-600 g/10 ares.

Suitable bipyridylium salts include the dichloride and dibromide of 1,1'-dimethyl-4,4'-bipyridylium or 1,1'-ethylene-2,2'-bipyridylium; that is,

Compound A:

1,1'-dimethyl-4,4'-bipyridylium dichloride ##STR5## Compound B: 1,1'-dimethyl-4,4'-bipyridylium dibromide

Compound C:

1,1'-ethylene-2,2'-bipyridylium dichloride ##STR6## Compound D: 1,1'-ethylene-2,2'-bipyridylium dibromide.

Suitable thiocarbamates include the following:

Compound 1:

S-benzyl-N,N-di-n-propylthiolcarbamate

b.p. 123°-125° C./0.015 mm Hg

Compound 2:

S-(4-methylbenzyl)-N,N-diethylthiolcarbamate

b.p. 107°-115° C./0.002 mm Hg

Compound 3:

S-(4-chlorobenzyl)-N-hexamethyleneiminocarbothiolate

m.p. 53°-55° C.

Compound 4:

S-(2-chlorobenzyl)-N,N-diethylthiolcarbamate

b.p. 136°-140° C./0.04-0.05 mm Hg

Compound 5:

S-(2.5-dimethylbenzyl)-N,N-dimethylthiolcarbamate

b.p. 130°-140° C./0.012 mm Hg

Compound 6:

S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate

b.p. 127°-131° C./0.012 mm Hg

The herbicidal compositions of this invention impart excellent herbicidal effects when applied to gramineous weeds, broadleaf weeds, perennial weeds and the like on agricultural areas such as upland fields, paddy fields, as well as orchards, and on non-agricultural areas. In applying the two active ingredients, it is also possible to prepare two compositions each containing one of the active ingredients of the bipyridylium salt and the thiocarbamate. The two compositions can then be combined in the application so as to produce a mixture in the above-mentioned ratio. The active ingredients can be applied using conventional techniques such as by adding a solid or liquid diluent or a surfactant and diluting with water.

Having now generally described the invention, a further understanding can be obtained by reference to certain specific Examples and Experiments, which are provided herein for purposes of illustration only and are not intended to be limiting in any manner unless otherwise specified.

PREPARATION OF COMPOSITION 1 Wettable Powder

40 wt. parts of Compound 1, 10 wt. parts of Compound B, 2 wt. parts of polyoxyethylenealkylarylether, 2 wt. parts of polyvinyl alcohol, 25 wt. parts of silicon dioxide and 21 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder.

Preparation of Composition 2 Emulsion

40 wt. parts of Compound 2, 10 wt. parts of Compound A, 10 wt. parts of polyoxyethylenealkyl phenol and 40 wt. parts of methanol were mixed and diluted with water to yield an emulsion.

Preparation of Composition 3 Wettable Powder

25 wt. parts of compound 3, 25 wt. parts of Compound C, 2 wt. parts of polyoxyethylenealkylarylether, 2 wt. parts of polyvinyl alcohol and 46 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder.

Preparation of Composition 4 Wettable Powder

30 wt. parts of Compound 4, 15 wt. parts of Compound D, 2 wt. parts of sodium alkylacrylsulfonate, 2 wt. parts of polyvinyl alcohol, 10 wt. parts of silicon dioxide and 41 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder.

Preparation of Composition 5 Emulsion

40 wt. parts of Compound 5, 5 wt. parts of Compound A, 7 wt. parts of polyoxyethylenealkylarylether, 3 wt. parts of calcium alkylbenzene sulfonate and 45 wt. parts of methanol were mixed and diluted with water to yield an emulsion.

The effect of the herbicidal compositions of this invention will be illustrated by certain experiments, which are not intended to be limiting unless otherwise specified.

EXPERIMENT 1

Manna-grass (height of 25 - 30 cm) and Pig weed (height of 25 - 30 cm) grown in pots of 100 cm² area were used for the experiments. The herbicidal compositions containing the amounts of the active ingredients specified in Table 1 were diluted with water. The diluted compositions were uniformly sprayed by a microsprayer at a rate of 100 liter/10 ares. The tests were performed twice in a greenhouse. After 15 days following the application, the weeds above the earth were cut, dried and weighed. The percentage of the weight of the dried weeds in the treated fields to that of the non-treated fields was calculated. Compositions prepared by mixing Compound A (an emulsion containing 24% of the active ingredient) or Compound D (an emulsion containing 30% of the active ingredient) and each of several thiocarbamates (an emulsion containing 50% of the active ingredient) in a tank were used. The applications of the compositions were conducted from 3:00 to 4:00 p.m. under an irradiation intensity of 30,000 Lux. The treating compositions and results are shown in Table 1.

                  Table 1                                                          ______________________________________                                                                   Manna-    Pig-                                       Active     Amount of      grass     weed                                       ingredient emulsions      (%)       (%)                                        ______________________________________                                                    A              5                                                    Compound A 200cc   +      400cc 2       5                                                 100     +      200   19      24                                     +           50     +      100   38      46                                     Compound 5  25     +       50   50      59                                                A              1                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   5       8                                      +           50     +      100   18      21                                     Compound 1  25     +      100   33      46                                                A              2                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   0       3                                      +           50     +      100   3       16                                     Compound 2  25     +      100   31      38                                                A              3                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   0       8                                      +           50     +      100   6       21                                     Compound 3  25     +       50   42      47                                                A              4                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   0       4                                      +           50     +      100   11      17                                     Compound 4  25     +       50   36      51                                                A              5                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   0       0                                      +           50     +      100   3       11                                     Compound 5  25     +       50   18      30                                                A              6                                                    Compound A 200cc   +      400cc 0       0                                                 100     +      200   0       0                                      +           50     +      100   5       8                                      Compound 6  25     +       50   12      16                                                D              1                                                    Compound D 200cc   +      400cc 0       0                                                 100     +      200   0       0                                      +           50     +      100   3       14                                     Compound 1  25     +       50   24      29                                                D              3                                                    Compound D 200cc   +      400cc 0       0                                                 100     +      200   0       1                                      +           50     +      100   5       15                                     Compound 3  25     +       50   29      26                                                D              6                                                    Compound D 200cc   +      400cc 0       0                                                 100     +      200   0       0                                      +           50     +      100   2       0                                      Compound 6  25     +        50  10      6                                                 800            92        100                                        Compound 1 400            100       100                                                   200            100       100                                                   100            100       100                                                   800            88        96                                         Compound 2 400            97        100                                                   200            100       100                                                   100            100       100                                                   800            93        97                                         Compound 3 400            98        100                                                   200            100       100                                                   100            100       100                                                   800            98        100                                        Compound 400                                                                              400            100       100                                                   200            100       100                                                   100            100       100                                                   800            89        90                                         Compound 5 400            97        96                                                    200            100       100                                                   100            100       100                                                   800            90        95                                         Compound 6 400            100       100                                                   200            100       100                                                   200            23        52                                         Compound A 100            40        67                                                     50            81        93                                                     25            100       100                                                   200            46        41                                         Compound D 100            63        56                                                     50            98        91                                                     25            100       100                                        Non-treatment                                                                             --             100       100                                        ______________________________________                                    

EXPERIMENT 2 Synergistic Effect (10 days following the application)

An orange orchard wherein various test weeds were uniformly grown was divided into blocks of dimension 2 m × 4 m. The herbicidal compositions containing amounts of the active ingredients as specified in Table 2 were diluted with water. The diluted compositions were sprayed at a rate of 100 liter/10 ares. After 10 days following the application, the herbicidal effects were observed. The weeds were Manna-grass (height of 40-50 cm); Smartweed (height of 50-70 cm); Hedge bindweed (height of 80-100 cm); and Cagratia japonice (height of 80-120 cm). The herbicidal effects are indicated using the following scale:

0: Number and height of the weeds is the same as that of the non-treated block.

1: 80% of the number or height of the weeds as compared with the non-treated block.

2: 60% of the number or height of the weeds as compared with the non-treated block.

3: 40% of the number or height of the weeds as compared with the non-treated block.

4: 20% of the number or height of the weeds as compared with the non-treated block.

5: weeds were completely dead.

The results are shown in Table 2.

                  Table 2                                                          ______________________________________                                         Concentration of                                                               active ingredients                                                                         Manna-   Smart-  Hedge   Cagratia                                  (ppm)       grass    weed    bindweed                                                                               japonice                                  ______________________________________                                         Compound A                                                                              720    3.0      2.5   3.0     3.0                                              360    1.5      1.0   1.5     2.0                                              180    0        0     0.5     0.5                                               90    0        0     0       0                                       Compound A                                                                     Compound C                                                                     A            6                                                                 400  +       1600   5      5     5       5                                     200  +        800   5      5     5       5                                     100  +        400   5      5     5       5                                      50  +        200   4.5    5     5       5                                     Compound 6                                                                              4000   0.5      0.5   0       0                                                2000   0        0     0       0                                                1000   0        0     0       0                                                 500   0        0     0       0                                       Non-treated block                                                                          0        0       0       0                                         ______________________________________                                    

EXPERIMENT 3 Regrowth Inhibition of Manna-grass

Manna-grass (height of 30 - 35 cm) grown in pots of 100 cm² was used for the experiment. The herbicidal compositions containing the amounts of the active ingredients shown in Table 3 were diluted with water. The diluted compositions were uniformly sprayed by a microsprayer at a rate of 100 liter / 10 ares during the evening and the treated pots were kept in a greenhouse. Watering was conducted by sucking water from the bottom of each pot. The herbicidal effects were observed and are indicated as in Experiment 2.

The results are shown in Table 3.

                  Table 3                                                          ______________________________________                                                          1 day   5 days  10 days                                                                              20 days                                 Concentration of after   after   after after                                   active ingredients                                                                              appli-  appli-  appli-                                                                               appli-                                  (ppm)            cation  cation  cation                                                                               cation                                  ______________________________________                                         Compound A                                                                               360        3.5     3.5   1     0                                               180        2       2     0     0                                                90        1.5     1.5   0     0                                                45        0.5     0     0     0                                     Compound A                                                                               A  6                                                                 +         400 + 800  5       5     5     5                                     Compound 6                                                                               200 + 400  5       5     5     5                                               100 + 200  5       5     5     4.5                                              50 + 100  5       5     4.5   3.0                                   Compound 6                                                                               4000       0.5     0.5   0     0                                               2000       0       0     0     0                                               1000       0       0     0     0                                     ______________________________________                                    

EXPERIMENT 4 Effect of Rain

The test of Experiment 2 was repeated except for the application of artificial rain at a rate of 200 mm/hr. after 15 minutes following the application of the herbicidal compositions. The next day, the herbicidal effects were observed.

The results are shown in Table 4.

                  Table 4                                                          ______________________________________                                                          Manna-      Manna-                                            Concentration of grass       grass                                             active ingredients                                                                              non-rain    artificial                                        (ppm)            block       rain block                                        ______________________________________                                         Compound A                                                                               720        4.5         3                                                       360        4           2                                                       180        3.5         1                                             Compound A                                                                               A   6                                                                          600 + 2400 5           5                                             +         300 + 1200 5           5                                                       150 +  600 5           5                                             Compound 6                                                                                75 +  300 5           4.5                                           Compound 6                                                                               4000       1.0         1.0                                                     2000       0           0                                                       1000       0           0                                             ______________________________________                                    

EXPERIMENT 5 Comparison of the effects of application at daytime versus those at evening

Manna-grass (height of 30-40 cm) grown in pots of 100 cm² was used for the experiment. The herbicidal compositions containing the amounts of the active ingredients specified in Table 5 were diluted with water. The diluted compositions were sprayed uniformly by a microsprayer at a rate of 10 liter/10 ares. The applications were conducted under an irradiation intensity of 50,000 lux of sunlight at daytime and a 2,500 lux at evening. After 5 days following the application, the herbicidal effects were observed and are indicated as in Experiment 2.

The results are shown in Table 5.

                  Table 5                                                          ______________________________________                                         Concentration of 50,000 lux  2,500 lux                                         active ingredients                                                                              irradiation irradiation                                       (ppm)            Manna-grass Manna-grass                                       ______________________________________                                         Compound A                                                                               720        4           4.5                                                     620        3           4                                                       180        1.5         3.5                                           Compound A                                                                               A    6                                                                         400 + 1600 5           5                                             +         200 +  800 5           5                                                       100 +  400 5           5                                             Compound 6                                                                                50 +  200 5           5                                             ______________________________________                                    

Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein. 

What is claimed as new and intended to be covered by letters patent is:
 1. A herbicidal composition, which consists essentially of:an effective amount of a mixture of a bypyridylium salt selected from the group consisting of the dichloride and dibromide salts of 1,1'-dimethyl-4,4'-bipyridylium and 1,1'-ethylene-2,2'-bipyridylium and a thiocarbamate having the formula: ##STR7## wherein R and R₁ each represent a lower alkyl group or which in combination with each other and with the nitrogen atom can form a hexamethyleneimino ring; R₂ represents ##STR8## X represents a halogen atom or a lower alkyl group, and n represents 0, 1 or 2 wherein the ratio of said bipyridylium salt to said thiocarbamate ranges from 1:1-30.
 2. The herbicidal composition of claim 1, which comprises the dichloride or dibromide salt of 1,1'-dimethyl-4,4'-bipyridylium and S-(4-chlorobenzyl)-N,N-diethylthiocarbamate as active ingredients.
 3. The herbicidal composition of claim 1, wherein X is a chlorine atom or a methyl group.
 4. The herbicidal composition of claim 1, wherein all alkyl groups contain from 1 - 7 carbon atoms.
 5. The herbicidal composition of claim 1, wherein the active ingredients are in the form of an emulsion.
 6. A method of controlling weeds, which comprises: applying to the locus thereof an effective amount of a diluted solution of the herbicidal composition of claim
 1. 7. The method of claim 6, wherein the herbicidal composition is applied to the foliage of the weeds.
 8. The method of claim 6, wherein the herbicidal composition is applied to the soil.
 9. The method of claim 8, wherein the amount of bipyridylium salt is 5-500 g/10 ares and the amount of the thiocarbamate is 50-1000 g/10 ares. 